201100449 六、發明說明： 【發明所屬之技術領域】 本發明關於光及紫外光安定劑，製造彼等之方法， 使用彼等之方法，其包含將安定劑添加至基質中，而且基 質係呈液態。 j 【先前技術】 光及紫外光安定劑防護材料（下文亦稱為基質）對抗 光化學降解。光化學降解主要由材料吸收光Η起，^ 促進電子至激發態，且於此電子激發態的材料可藉由化學 鍵斷裂或形成而反應。此初次光誘發之化學反應可造成包 含基質或材料分子變化的二次反應，料此等反應於此= 害材料的物理性質，造成例如粉化、黃化、光澤損 裂縫或裂縫形成。 ’ 因此，㊉見的實務係將光安定劑添加至用於製造塑 物體、膜或表面塗層之材料中，此係假如彼等暴露於光， 光及紫外（uv)光時。在通常不遭受光化學降 的金屬例子中，沒有必要使用光安定劑，其係由於复中 電，處於被稱為價及導電帶的能態之其特殊結構。然而， 二:分或所有其他材料，特別為有機材料易受到輻射作用 (诸如光）的損害。 面層入t光（包括紫外光）常僅穿透任何厚實本體的表 因為光在材料中散射，其甚至發生在透明 用於防護材料對抗不希望的光作用之常見方法 201100449 加安定劑，亦即吸收光至與欲防護之材料相比為提升程度 且使吸收的能量以熱（振動能）形式耗散於材料内的物質。 安定劑平均地分佈於材料内部，且此安定劑的主要部分因 此不易接受光作用，而因此未被使用。 在與本發明有關的研究中，頃發現集中於欲防護之材 料的表面層中的安定劑使安定劑達到更好的應用，且增加 關於所使用之安定劑量的效率。 光安定劑固著於聚稀膜表面已從下列已知：，，A n〇vel photoadditive for polyolefin photostabilisation: Hindered201100449 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to light and ultraviolet stabilizers, and methods of making same, using the method comprising adding a stabilizer to a matrix, and the matrix is in a liquid state . j [Prior Art] Light and UV stabilizers (hereinafter also referred to as substrates) resist photochemical degradation. Photochemical degradation is mainly caused by the absorption of light by the material, which promotes electrons to the excited state, and the material of this electronically excited state can be reacted by chemical bond cleavage or formation. This primary light-induced chemical reaction can cause a secondary reaction involving changes in the matrix or material molecules, which are responsible for the physical properties of the material, such as chalking, yellowing, gloss damage cracking or crack formation. Therefore, the practice of the Ten Commands is to add light stabilizers to materials used to make plastics, films or surface coatings if they are exposed to light, light and ultraviolet (uv) light. In the case of metals which are generally not subjected to photochemical degradation, it is not necessary to use a light stabilizer which, due to the complex charge, is in a special structure called the energy state of the valence and the conduction band. However, two or all other materials, especially organic materials, are susceptible to radiation (such as light) damage. The surface layer of t-light (including ultraviolet light) often penetrates only the surface of any thick body because light scatters in the material, which even occurs in the transparent method used to protect the material against unwanted light. 201100449 plus stabilizer, also That is, the light is absorbed to a level that is elevated compared to the material to be protected and that the absorbed energy is dissipated into the material in the form of heat (vibration energy). The stabilizer is evenly distributed inside the material, and the main part of the stabilizer is therefore less susceptible to light and is therefore not used. In the studies relating to the present invention, it has been found that stabilizers concentrated in the surface layer of the material to be protected provide a better application of the stabilizer and increase the efficiency with respect to the dosage of the stabilizer used. The light stabilizer is fixed to the surface of the thin film and has been known from the following:,, A n〇vel photoadditive for polyolefin photostabilisation: Hindered
amine light stabiliser” by DESAI Shrojal M.，PANDEYAmine light stabiliser” by DESAI Shrojal M.,PANDEY
Jitendra K., and SINGH R. P., «Die MakromolekulareJitendra K., and SINGH R. P., «Die Makromolekulare
Chemi - Macromolecular symposia，，，Eurofillers ,99 Conference，vol. 169, pp. 121 to 128，其中受阻胺光安定劑 係藉由1，2,2,6,6-五甲基底唆基-4-丙稀酸g旨直接光接枝於表 面上’或藉由1，2,2,6,6 -五甲基-4-娘咬醇與丁二酸針官能化 之聚浠表面反應而經表面固定於聚乙稀及聚丙烯薄膜。 此方法包含複雜的額外處理步驟，其中欲防護之聚合 性物件必須藉由將安定劑以化學鍵聯於聚合物表面而修 改。若僅一部分的聚合物分子根據此等先前技術文件予以 修改，且將此等經修改之聚合物分子摻合至未經修改之聚 合物中，用於熔融法中的後續成形時，諸如射出模製、擠 壓或旋轉模製，則經修改之聚合物變成均勻地分佈於以此 熔融法成形之聚合性物件内部，正如只添加無聚合物結合 之安定劑的例子。若希望安定劑集中於表面附近或表面 5 201100449 上’則最終物件的表面處 甘—a 性物件w…其包含在成形聚合 =°、、纖維、瓶或射出模製物件）之後額外的 步：，，本發明的目的係提供一種光安定劑類別，： 定劑集中於欲防護之材料的表面區㉟，不包含此二 額外的表面修改步驟。 【發明内容】 、此目的已藉由提供分佈在材料内部的表面活性或兩親 光安疋d來實現，且此材料呈液態。兩親性光安定劑包 含表面活性或兩親性部分，其造成安定劑在表面形成過程 期間向該材料的表面移動及材料固化，及安定部分s，其為 =學活性成分且轉換人射光能量成為在材料内耗散的振 動能或熱能。兩個部分係以呈單或多鍵或至少二價橋連基 團之形式的化學鍵連接。 本發明因此關於表面活性或兩親性光安定劑as，其包 含具有表面活性或兩親性特質的結構部分A及能夠吸收可 見光及紫外光的結構部分S。 本發明亦關於-種包含黏合劑B及表面活性或兩親性 光安定劑AS之塗料組成物，在塗料組成物交聯及固化而於 基質上形成塗膜時，該光安定劑細在與該塗膜表面直接 相鄰的層中之表面活性或兩親性光安定劑As之質量分率比 在塗膜中心、的層中之表面活性或兩親性光安定劑as之質量 分率多至少10%的方式移動至該膜的表面。 201100449 【實施方式】 就本發明的目的而言，以與塗膜的表面直接相鄰的層 意謂從不與基質接觸的塗膜表面向表面之下延伸至多 微米深度之層。 —在塗膜層中的光安定劑之質量分率可以尋常的方式測 疋’特別使用光譜法，諸如IR、UV及質譜法。 Ο Ο 以表面活性〃意謂化合物或組成物在摻合至物質時 改變該物質的表面張力，其係以該物質的表面張力與包含 該物質及表面活性化合物或組成物之混合物的表面張力不 同的方式改變。表面活性部分較佳為聚合物或寡聚物，較 佳為可以基引發之乙烯基型聚合法所形成者。 若分子具有以群聚之立體環境圍繞的胺宫能基，則分 =稱具有受阻胺結構，其在文獻中亦被稱為、、位阻胺' :兩香族環以幾基>C=〇連接，則分子據稱且有1 二=構„。若有一具有兩個相鄰的碳原子為另-芳香族環 、二唑環（具有三個氮原子在環中以、 員環），則分子據稱且有苯并一 ^ ，，3-順序的5- 的氮原子於6-員芳香旄右有二個不相鄰 貝方香族％中，則分子據稱具有 個部分：―具其與7二性部^ 物（特別為塗料組合物中的^料組成 :聚合物與對應於混合物中的該第-部合劑 物包含至多5%之質量-子（該處合 滿合物令沒有可見的相八應於該第-部分之分子）的 見的相分離效果時，則此部分C被視為可 7 201100449 相容。安定劑AS之表面活性部分A的第二部分N與黏合 劑或聚合物不相容，且若混合比允許，則形成與黏合劑或 聚合物分離的相。 若氫原子或甲基添加至基中形成—部分時，則分子據 稱對應於此部分。較佳者，在可相容系統中未觀察到相分 離的質量分率至多為1〇%。可見之相分離係由可以肉眼觀 察到在混合物中形成分離層或發生混濁所顯示。在聚合物 中，諸如熱塑性樹脂，相分離亦可藉由顯示於微差掃瞄熱 1 a十中不同的轉換溫度或以扭轉擺而偵測。 若將對應於兩親性部分的第二部分N之分子與聚合物 或黏合劑混合’以形成對應於兩親性部分A的第二部分N 之分子佔至少5%之質量分率的均勻熔融或液體混合物在 混合之後24小時或更少的時間之後，此混合物在保持與混 合所使用之相同溫度下將形成分離相。分離相的形成係可 以肉眼偵測到巨觀的相分離或發生混濁所顯示。 根據本發明的安定劑As之安定部分§較佳地從熟知的 光或糸外光安定劑衍生而來，較佳地以所謂的受阻胺、以 具有:苯基酮結構之分子、以具有苯並三唑結構之分子及 具有三畊結構之分子為基準。在本發明 街…部分1謂氣原子或甲基從分子（在此例子中係 先女疋劑分子）斷裂以得到基，其於是被稱為、'一部分〜 可將(2-羥基-4-甲氧基苯基苯基甲_ (亦以其俗名 乳=酮稱之）的3，-位置上的氫原子移走，以形成在此 可以 '、氧苯酮之一部分〃稱呼的基。 201100449 根據本發明的光安定劑AS之安定部分s及兩親性或表 面活性部分A係以至少二價橋鍵聯在一起，與表面活性或 兩親性部分A形成至少-個化學鍵及與安定部分s形成至 少一個化學鍵。至少二價橋連基團較佳地包含至少—種式 -CRiR^CI^R4-之結構，其中_Ri、_R2、_R3及r4基中任何 一個可彼此獨立為-H、-F、_cn、_CH3、_〇H、_〇CH3、烷基Chemi - Macromolecular symposia,,, Eurofillers, 99 Conference, vol. 169, pp. 121 to 128, wherein the hindered amine light stabilizer is made up of 1,2,2,6,6-pentamethylguanidino-4- Acrylic acid g is directly photo-grafted onto the surface' or by surface reaction of 1,2,2,6,6-pentamethyl-4-nitrile with a succinic acid-functionalized polyfluorene surface Fixed to polyethylene and polypropylene film. This method involves a complex additional processing step in which the polymeric article to be protected must be modified by chemically bonding the stabilizer to the polymer surface. If only a portion of the polymer molecules are modified according to such prior art documents, and such modified polymer molecules are incorporated into the unmodified polymer for subsequent formation in a melt process, such as an injection mold By molding, extrusion or rotational molding, the modified polymer becomes uniformly distributed inside the polymerizable article formed by the melt method, just as an example in which only a polymer-free stabilizer is added. If it is desired that the stabilizer be concentrated near the surface or on the surface 5 201100449, then the surface of the final object at the surface of the final object w... which is included in the shaped polymerization = °, fiber, bottle or injection molded article) additional steps: The object of the present invention is to provide a class of light stabilizers which: the concentration agent concentrates on the surface area 35 of the material to be protected, and does not include these two additional surface modification steps. SUMMARY OF THE INVENTION This object has been achieved by providing a surface active or amphiphilic optical ampule d distributed inside a material, and the material is in a liquid state. The amphiphilic light stabilizer comprises a surface active or amphiphilic moiety which causes the stabilizer to move to the surface of the material during the surface formation process and to solidify the material, and a stable portion s which is an active ingredient and converts the human light energy Becomes vibrational or thermal energy that is dissipated within the material. The two moieties are linked by a chemical bond in the form of a single or multiple bond or at least a divalent bridging group. The present invention thus relates to a surface active or amphiphilic photo-stabilizer as comprising a moiety A having a surface active or amphiphilic character and a moiety S capable of absorbing visible light and ultraviolet light. The invention also relates to a coating composition comprising a binder B and a surface active or amphiphilic light stabilizer AS. When the coating composition is crosslinked and cured to form a coating film on the substrate, the light stabilizer is fine The surface activity of the directly adjacent layer on the surface of the coating film or the mass fraction of the amphiphilic light stabilizer As is higher than the surface activity in the center of the coating film or the mass fraction of the amphiphilic light stabilizer as Move to the surface of the film by at least 10%. [Embodiment] For the purpose of the present invention, a layer directly adjacent to the surface of the coating film means a layer extending from below the surface of the coating film which is not in contact with the substrate to a depth of a plurality of micrometers. - The mass fraction of the light stabilizer in the coating layer can be measured in an ordinary manner by special use of spectroscopic methods such as IR, UV and mass spectrometry. Ο Ο a surface active 〃 means that the compound or composition changes the surface tension of the substance when it is blended into the substance, which is different from the surface tension of the substance and the surface active compound or mixture of the composition. The way to change. The surface active moiety is preferably a polymer or oligomer, preferably formed by a vinyl-based polymerization process which can be initiated. If the molecule has an amine ruthenium group surrounded by a clustered stereo environment, the fraction = has a hindered amine structure, which is also referred to in the literature as a sterically hindered amine: a two-fragrance ring with a few bases > C = 〇 connection, the molecule is said to have 1 = = „. If there is one with two adjacent carbon atoms is another aromatic ring, diazole ring (with three nitrogen atoms in the ring, ring) , the molecule is said to have a benzo-, ^, 3-order 5-a nitrogen atom in the 6-membered aromatic 旄 right two non-adjacent Bayan fragrant%, the molecule is said to have a part: ―Having it and the bisector (in particular for the composition of the coating composition: the polymer and the first part of the mixture corresponding to the mixture contains at most 5% of the mass--(the place is full When the phase of the phase is not visible, the phase separation effect seen by the molecule of the first part is considered to be compatible with the phase 7 201100449. The second part of the surface active portion A of the stabilizer AS Incompatible with the binder or polymer, and if the mixing ratio permits, a phase separate from the binder or polymer is formed. If a hydrogen atom or methyl group is added to When a part is formed in the base, the molecule is said to correspond to this part. Preferably, the mass fraction of phase separation is not observed in the compatible system at most 1%. The visible phase separation can be observed by the naked eye. As shown by the formation of a separation layer in the mixture or the occurrence of turbidity. In polymers, such as thermoplastic resins, phase separation can also be detected by displaying different conversion temperatures in the differential scanning heat 1 a ten or by twisting the pendulum If the molecule corresponding to the second portion N of the amphiphilic moiety is mixed with the polymer or binder to form a uniformity of the mass fraction of at least 5% of the molecule corresponding to the second portion N of the amphiphilic moiety A The molten or liquid mixture, after 24 hours or less after mixing, will form a separate phase at the same temperature as that used for mixing. The formation of the separated phase can detect macroscopic phase separation or occurrence by the naked eye. Shown by turbidity. The stable portion of the stabilizer As according to the present invention is preferably derived from a well-known photo or ruthenium stabilizer, preferably a so-called hindered amine, having a phenyl ketone structure. Based on the molecule having a benzotriazole structure and a molecule having a three-till structure. In the street of the present invention, part 1 is a gas atom or a methyl group is broken from a molecule (in this case, a daughter-in-law molecule). The base is obtained, which is then referred to as 'partial~' a hydrogen atom at the 3,-position of (2-hydroxy-4-methoxyphenylphenylmethyl) (also known by its common name milk = ketone) Removed to form a group which can be referred to herein as a part of oxybenzone. 201100449 The stable portion s of the light stabilizer AS according to the present invention and the amphiphilic or surface active moiety A are linked by at least a bivalent bridge. Together, it forms at least one chemical bond with the surface active or amphiphilic moiety A and at least one chemical bond with the stable moiety s. The at least divalent bridging group preferably comprises at least one of the formulas - CRiR^CI^R4- a structure in which any one of _Ri, _R2, _R3 and r4 groups may independently be -H, -F, _cn, _CH3, _〇H, _〇CH3, alkyl
-CnH2n+1、氧烷基_〇_cnH2n+1，其中n於每個例子中獨立為 從2至18、芳基及氧芳基。此結構可與安定部分直接鍵結， 且二價橋亦可包含額外的酯結構_〇_c〇_、胺甲酸乙酯基團 -NH-CO-、尿素基團_NH_co_NH_或2經基-π伸丙義 -CH2-CH(〇H)-CH2-或其任何組合。鍵聯較佳地藉由添加^ 安定部分之結構經由撓性間隔基團連接的羧酸基團或脂族 羥基而達成，及藉由添加烯屬不飽和官能而達成，該添加 係經由例如酸官能與縮水甘油（甲基）丙烯酸酯在酯鍵形成 下的反應，或羥基官能與1莫耳（甲基）丙烯酸與丨莫耳二異 氰酸酯之反應產物在胺甲酸乙酯鍵形成下的反應。 本發明更多較佳的具體實例詳述於申請專利範圍中。 包含表面活性或兩親性光安定劑AS之材料較佳為包含 黏合劑B之塗料組成物，其中表面活性或兩親性光安定劑 AS均勻地分散於塗料組成物中。在塗布基質時，膘係由塗 料組成物的材料於基質上所形成。在以蒸發溶劑（其可為 有機溶劑或水）的膜形成期間，塗料組成物的親水性或疏 水性特質受到改變。此變化在塗料組成物中的水性分散2 黏合劑中特別顯著。在此例子中，兩親性光安定劑as之兩 9 201100449 親性部分A的適當選擇係由與聚合性黏合劑B或聚合物可 相容之部位C(在可熔融加工之聚合物的安定化例子中，特 別為一種具有相同或非常類似的化學結構）及—個與聚合 性黏合劑（特別具有不同的化學結構）不形成均句的混合 物之部位N建立兩親性部分。 頃發現一些為二或多個化學結構不同的單體之共聚物 的聚合物可充當根據本發明的安定劑As之兩親性部分A。 這些實例為具有從氟單體（諸如氟化醇及烯屬不飽和酸之 酉曰）彳厅生之具有含氟結構的乙烯基共聚物。具有在本發明 上下文中的兩㈣質的其他共聚物為具有_基或酸官能基 團之丙烯酸共聚物，諸如烯屬不飽和酸本身，較佳為丙烯 酸或甲基丙烯酸’或其與多元醇之酯’較佳為丙烯酸羥乙 酯或甲基丙烯酸羥乙酯。包含至少一個與欲安定之聚合物 可相容之鏈段及至少_個形成分離相之鏈段的嵌段共聚物 亦有用於本發明，且於熱塑性或熱固性聚合物的例子中特 別佳。 類^於表面活性或兩親性光安定劑朝向塗膜表面移動 的效果可在用於塗料的可輻射固化之黏合劑中觀察到。在 此表面活十生或兩穿見性部分的豸擇必須使得形&可轄射固化 之塗料、.且成物的單體或寡聚性黏合劑分子與表面活性或兩 親性光安定劑AS形成均句的溶液或分散液。在以照射濕塗 -誘發聚合時’聚合物形成造成表面活性„親性光安 疋劑的容解度下降’該溶解度下降亦造成表面活性或兩親 f生光女疋劑在形成過程中朝向塗膜表面移動。 201100449 另-類似的效果可在由固化時結晶之熱塑性聚合物 .(諸如聚烯’聚酯、聚醯胺或聚縮醛）製成之物體的光穩 定化中實現。藉由選擇表面活性或兩親性光安定劑之表面 活性或兩親性部分使得肖固化熱錢聚合物僅有弱的共結 晶傾向，光安定劑亦朝向物體表面滲出。此傾向亦可藉由 添加成核劑至聚合物中而增加，其促進結晶且由此促進表 面活性或兩親性光安定劑As的移動。 ㈣的效果可在從粉末塗料組成物製備之塗料中觀察 到：在基質上的膜固化時’且在以結晶狀聚合物為基之粉 末塗料黏合劑的例子中特別明顯，光安定劑朝向表面滲 出。可藉由塗覆粉末塗料於其表面上比周圍更冷的基質而 促進滲出。接著光安定劑優先集中於仍為液體之區帶，因 此進一步增強表面活性光安定劑入8朝向塗膜的表面移動。 A安定劑之使用j法的較佳具體實例因此包含將該安 定劑添加至熱塑性聚合物中，該安定劑係以該熱塑性聚合 Q物與該光安定劑之質量總和為基準計從0.1%至5%之質量 分率添加，將該熱塑性聚合物與該光安定劑之混合物溶 融，將熔融混合物混合，及將熔融混合物以冷卻固化。 光安定劑之使用方法的另一較佳具體實例因此包含將 該安定劑添加至熱固性聚合物材料中，該安定劑係以該熱 固性聚合物材料與該光安定劑之質量總和為基準計從 至5%之質量分率添加，將該熱固性聚合物材料與該光安定 劑之混合物加熱至低於該熱固性聚合物之固化溫度的溫 度，將溶融混合物混合，及將炫融混合物以加熱至等於或 11 201100449 大於該熱固性聚合物材料之固化溫度的溫度而固化。 光女疋劑之使用方法的另一較佳具體實例因此包含將 該安定劑添加至溶解在有機溶劑中的可交聯之聚合性黏合 劑中，該安定劑係以該可交聯之聚合性黏合劑與該光安定 劑之質量總和為基準計從G 1%至5%之質量分率添加，以 形成塗料組成物，將該塗料組成物混合將混合之塗料組 成物塗覆於基質，在基質上形成膜，將經塗布之基質加熱 至足以除去至少一部分溶劑的溫度，及將該基質上的該膜 以加熱或使經塗布之基質接受輻射而交聯。 光安定劑之使用方法的另一較佳具體實例因此包含將 該安定劑添加至分散或乳化於水中的τ交聯之聚合性黏合 劑中，該安定劑係以該可交聯之聚合性黏合劑與該光安定 劑之質量總和為基準計從0丨％至5%之質量分率添加以 形成塗料組成物，將該塗料組成物混合，將混合之塗料組 成物塗覆於基質，在基質上形成膜，將經塗布之基質加熱 至足以除去至少一部分溶劑的溫度，及將該基質上的該膜 以加熱或使經塗布之基質接受輻射而交聯。 本發明以下列的實施例進一步解釋，其不被理解為限 制。 實施例1 :聚合性光安定劑之製備 將50公克異丙醇裝入配備回流冷凝器、攪拌器及兩個 進料幫浦之具有500毫升容積的玻璃反應器中。將内容物 加熱至回流’並經2小時逐漸添加〇·7公克第三戊基過氧基 (2-乙基己酸酯）（⑧LUpersol 575，Pennwalt Corp· ) 、140 12 201100449 公克乙酸乙酯、另外5公♦里； ^ A克異两醇、50.1公克丙烯酸丁酯、 22.8公克丙烯酸2-乙基己醋鱼％ \ + 〇 土已酉曰與26公克（2-羥基-4-[2-丙烯氧 基]-乙虱基苯基）-苯基甲酮Γ — (種稀屬不飽和取代之二苯基 酮）之混合物。將混合物在糌拄 长視拌下保持在回流溫度下另外1 小時，並接著將0.6公克第三戊基過氧基(2_乙基己酸醋)、5 公克異丙酵、21.4公克丙烯酸丁醋與97公克丙烯酸2_乙基 己酉旨之弟二混合物在^ 3L AL ^ ^ 卜 小¥期間内添加至反應混合物-CnH2n+1, oxyalkyl_〇_cnH2n+1, wherein n is independently from 2 to 18, aryl and oxyaryl in each case. The structure may be directly bonded to the stable moiety, and the divalent bridge may also contain an additional ester structure _〇_c〇_, an urethane group-NH-CO-, a urea group _NH_co_NH_ or a 2-base group. - π-extended -CH2-CH(〇H)-CH2- or any combination thereof. The bonding is preferably achieved by adding a carboxylic acid group or an aliphatic hydroxy group to which the structure of the anchoring moiety is attached via a flexible spacer group, and by adding an ethylenically unsaturated functional group, for example, by adding an acid. The reaction of a functional group with a glycidyl (meth) acrylate in the formation of an ester bond, or a reaction of a hydroxy function with a reaction product of 1 mol (meth)acrylic acid and decyl diisocyanate under the formation of a urethane bond. More preferred specific examples of the invention are detailed in the scope of the patent application. The material comprising the surface active or amphiphilic light stabilizer AS is preferably a coating composition comprising the binder B, wherein the surface active or amphiphilic light stabilizer AS is uniformly dispersed in the coating composition. When the substrate is coated, the lanthanide is formed on the substrate from the material of the coating composition. The hydrophilicity or hydrophobic character of the coating composition is altered during film formation with an evaporating solvent which may be an organic solvent or water. This change is particularly pronounced in the aqueous dispersion 2 binder in the coating composition. In this example, the amphiphilic light stabilizer as the two 9 201100449 is selected from the hydrophilic part B compatible with the polymerizable adhesive B or the polymer (the stability of the melt processable polymer) In the case of the example, in particular, a chemical moiety having the same or very similar chemical structure and a site N which is a mixture of a polymeric binder (especially having a different chemical structure) does not form a homologous sentence. It has been found that some polymers which are copolymers of two or more chemically different monomers can serve as the amphiphilic moiety A of the stabilizer As according to the invention. These examples are vinyl copolymers having a fluorine-containing structure derived from a fluorine monomer such as a fluorinated alcohol and an ethylenically unsaturated acid. Other copolymers having two (tetra) qualities in the context of the present invention are acrylic copolymers having a benzyl or acid functional group, such as an ethylenically unsaturated acid per se, preferably acrylic acid or methacrylic acid or a polyol thereof The ester 'is preferably hydroxyethyl acrylate or hydroxyethyl methacrylate. Block copolymers comprising at least one segment compatible with the polymer to be stabilized and at least one segment forming the separated phase are also useful in the present invention and are particularly preferred in the case of thermoplastic or thermoset polymers. The effect of surface-active or amphiphilic light stabilizers moving toward the surface of the coating film can be observed in radiation-curable adhesives for coatings. The choice of living the surface or the two visible parts of the surface must be such that the shape & can cure the cured coating, and the monomer or oligomeric binder molecules of the composition and the surface active or amphiphilic light stabilizer The agent AS forms a solution or dispersion of the homologous sentence. In the case of irradiation with wet coating-induced polymerization, 'polymer formation causes surface activity „The degree of solubility of the hydrophilic photoamperifier decreases.' The decrease in solubility also causes surface activity or the orientation of the amphiphilic sputum in the formation process. The surface of the coating film moves. 201100449 Another-similar effect can be achieved in the light stabilization of an object made of a thermoplastic polymer that crystallizes upon curing, such as polyene polyester, polyamine or polyacetal. By selecting the surface active or amphiphilic portion of the surface active or amphiphilic light stabilizer, the Xiao-cured hot money polymer has only a weak tendency to co-crystallize, and the light stabilizer also oozes toward the surface of the object. This tendency can also be added by The nucleating agent increases into the polymer, which promotes crystallization and thereby promotes surface activity or movement of the amphiphilic light stabilizer As. (4) The effect can be observed in a coating prepared from a powder coating composition: on a substrate When the film is cured' and is particularly evident in the example of a crystalline polymer-based powder coating binder, the light stabilizer oozes toward the surface. It can be coated on the surface by a powder coating. The cold matrix promotes bleed. The photo-stabilizer is then preferentially concentrated on the still liquid zone, thus further enhancing the surface-active light stabilizer into the surface of the coating film. A preferred embodiment of the use of the stabilizer Therefore, the stabilizer is added to the thermoplastic polymer, and the stabilizer is added in a mass fraction of 0.1% to 5% based on the total mass of the thermoplastic polymerized Q and the light stabilizer, and the thermoplastic is polymerized. Melting the mixture with the light stabilizer, mixing the molten mixture, and solidifying the molten mixture by cooling. Another preferred embodiment of the method of using the photosensitizer thus comprises adding the stabilizer to the thermosetting polymer material, The stabilizer is added from a mass fraction of 5% to the total mass of the thermosetting polymer material and the light stabilizer, and the mixture of the thermosetting polymer material and the light stabilizer is heated to be lower than the thermosetting property. The temperature at which the polymer cures, mixes the molten mixture, and heats the mixture to a temperature equal to or 11 201100449 greater than the thermoset Another preferred embodiment of the method of using the photon tanning agent comprises adding the stabilizer to the crosslinkable polymerizable binder dissolved in an organic solvent, which The stabilizer is added from a mass fraction of G 1% to 5% based on the total mass of the crosslinkable polymerizable binder and the light stabilizer to form a coating composition, and the coating composition is mixed. A mixed coating composition is applied to the substrate to form a film on the substrate, the coated substrate is heated to a temperature sufficient to remove at least a portion of the solvent, and the film on the substrate is heated or the coated substrate is irradiated Crosslinking. Another preferred embodiment of the method of using the photosensitizer thus comprises adding the stabilizer to the τ crosslinked polymeric binder dispersed or emulsified in water, the stabilizer being crosslinked The mass ratio of the polymerizable binder to the light stabilizer is from 0% to 5% by mass to form a coating composition, the coating composition is mixed, and the mixed coating composition is mixed. Overlying the substrate, a film is formed on the substrate, heated to a temperature sufficient to remove at least a portion of the solvent of the coated substrate, and the film on the substrate to heat the coated substrate or to receiving radiation crosslinking. The invention is further illustrated by the following examples which are not to be construed as limiting. Example 1: Preparation of a polymerizable light stabilizer 50 g of isopropyl alcohol was charged into a glass reactor having a volume of 500 ml equipped with a reflux condenser, a stirrer and two feed pumps. The contents were heated to reflux' and gradually added 〇7 g of a third amyl peroxy (2-ethylhexanoate) (8 LUpersol 575, Pennwalt Corp.), 140 12 201100449 g of ethyl acetate, over 2 hours. Another 5 ♦ ♦ Lane; ^ A grams of isoamyl alcohol, 50.1 grams of butyl acrylate, 22.8 grams of 2-ethylhexyl acrylate fish% \ + 〇 酉曰 酉曰 and 26 grams (2-hydroxy-4-[2- A mixture of propyleneoxy]-ethenylphenyl)-phenylmethanone oxime (a dibasic unsaturated substituted diphenyl ketone). The mixture was kept at reflux temperature for an additional hour under a mixture of sorghum and then 0.6 g of a third amyl peroxy group (2-ethylhexanoic acid vinegar), 5 g of isopropyl alcohol, 21.4 g of butyl acrylate. The mixture of vinegar and 97 grams of acrylic acid 2-ethylhexidine is added to the reaction mixture during the period of ^ 3L AL ^ ^ Bu Xiao ¥
中。反應接著藉由將混合物保持在回流溫度下1又半小時 以上而達到①成’且最終將殘餘單體、溶劑及來自基起始 劑分解的副產物在減壓下以蒸餾移出。將所得聚合物冷卻 至65 C且經由具有25微米孔徑之濾器過濾。所獲得具有 99.1%之產率的聚合物為淺黃色且有黏性，並具有η 2公 2/莫耳之重量平均莫耳質量，如以凝膠滲透層析術使用聚 苯乙烯標準所測定。聚合物被稱為、、uv_ i 〃。在此聚合物 中的2-羥基二苯甲酮部分之質量分率為2〇%。 實施例2 :以矽氧烷改良之聚合性光安定劑之製備 將50公克異丙醇裝入配備回流冷凝器、攪拌器及兩個 進料幫浦之具有500毫升容積的玻璃反應器中。將内容物 加熱至回流，並經2小時逐漸添加〇.7公克第三戊基過氧基 (2-乙基己酸酯）（®LUpers〇i 575，Pennwalt Corp. ) 、140 公克乙酸乙酯、另外5公克異丙醇、50.1公克丙烯酸丁酯、 2〇公克丙烯酸2-乙基己酯、3.9公克以乙烯基終止之聚矽氧 燒與26公克（2-羥基-4-[2-丙烯氧基]-乙氧基苯基）-苯基甲酮 (一種烯屬不飽和取代之二苯基酮）之混合物。將混合物 13 201100449 在攪拌下保持在回流溫度下另外1小時，並接著將〇·6公克 第二戊基過氡基（2_乙基己酸酯）、5公克異丙醇、21.4公克 丙稀酸丁醋與8.6公克丙烯酸2-乙基己酯之第二混合物在 另外2小時期間内添加至反應混合物中。反應接著藉由將 混合物保持在回流溫度下1又半小時以上而達到完成，且 最終將殘餘單體、溶劑及來自基起始劑分解的副產物在減 壓下以蒸餾移出。將所得聚合物冷卻至65。(：且經由具有25 微米孔桎之濾器過濾。所獲得具有98.8%之產率的聚合物 為淺黃色且有黏性，並具有125公斤/莫耳之重量平均莫耳 質莖，如以凝膠滲透層析術使用聚苯乙烯標準所測定。聚 合物被稱為、UV_2〃 。在此聚合物中的2_羥基二笨甲_部 分之質量分率為20%。 實施例3 :塗料之製備 以丙烯酸黏合劑樹脂為基之塗料組成物係根據表1之 調配物製備。將這些組成物以實施例1和2(UV-1和Uv_2) 之聚合性安定劑及以習知的二苯基酮型光安定劑（，，比較 性，2-羥基_4_(2_乙基乙氧基）_二苯基酮）安定，包括作為 參考的未安定化之樣品。將這些塗料組成物塗覆於曾接受 CED (陰極電沉積）底漆處理及白色底漆膜之冷軋鋼薄片， 在14(TC經3〇分鐘乾燥之後得到從牦微米至5〇微米 密耳至2.〇密耳）之乾膜厚度。 14 201100449 表1 : A至D之塗料調配物 組分+ A B C 丙烯酸樹脂* 75公克 75公克 75公克 75公克 三聚氰胺交聯劑 樹脂++ 25公克 25公克 25公克 25公克 酸觸媒（DDBSA) $ 0.7公克 0.7公克 0.7公克 0.7公克 UV-1 (實施例1) 1公克 0 0 0 UV-2 (實施例2) 0 1公克 0 0 比較性光安定劑 0 0 2公克 0 HALSQ 1公克 1公克 1公克 0 〇 +將丁醇（15公克）、二曱苯（18公克）與PM乙酸酯（丙 二醇單曱醚乙酸酯，18公克）之溶劑混合物添加至所有的 調配物中 *溶解在烷基化芳香族之混合物中的羥基官能性丙烯酸樹 脂-® Solvent Naphtha，65%之質量分率的固體，22毫克/ 公克之酸值，120毫克/公克之羥基值 ++高度甲基化三聚氰胺甲醛樹脂，在25°C下3800 mPa.s， 少於0.3%之質量分率的游離曱醛 〇 $ DDBSA=十二烷基苯磺酸 α 1，2,2,6,6-五甲基-4-哌啶醇之單-及雙-酯與癸二酸之混合 物（®Tinuvin 262，Ciba Specialty Chemicals Inc.) 2-羥基二苯基酮部分之質量分率就塗料組成物a和B 二者為0.2%及就塗料組成物C為2.0%。組成物D為未安 定化之控制組。 使這些塗布之鋼板（以塗料組成物A塗布之鋼板A， 以塗料組成物B塗布之鋼板B ’以塗料組成物c塗布之鋼 15 201100449 板C ’以塗料組成物D塗布之鋼板D )接受依照ASTM G 1 5 5 之氙对候試驗（在0.3 5瓦特/平方公尺及（6 3 ± 3 ) °C下；照 射102分鐘及接著照射與水噴霧18分鐘之循環）。在塗膜 中的黃化變化係在指定之暴露時間之後監控，將結果收集 於表2中。 黃化（△ b )係以慣用的儀器（b YK Gardner分光光度 計）測量且根據ASTM E 3 1 3計算。 表2 :在照射之後的黃化變化（Δ b) 在右列時間 之後的Ab 500 小時 1000 小時 1500 小時 2000 小時 3000 小時 4000 小時 5000 小時 鋼板A 0.09 0.29 0.34 0.49 0.6 0.8 0.94 鋼板B 0.1 0.35 0.37 0.49 0.6 0.7 0.88 鋼板C 0.35 0.66 0.73 0.91 1.2 1.4 1.67 鋼板D 0.56 1.31 2.06 3.39 8.4 不4 卜格 可觀察出雖然在塗料組成物A和B中的安定結構2-羥 基二苯基酮的質量分率僅為塗料組成物C (在此為2 〇%之 質ΐ分率）的1 〇% ’但是在包含習知的紫外光安定劑之塗 料組成物中對抗由紫外光所引起之黃化的防護遠低於根據 本發明的紫外光安定劑之例子中於塗料組成物Α和Β中的 該防護。 實施例4 :以笨并三唑為基之聚合性光安定劑之製備 將70公克異丙醇裴入配備回流冷凝器、攪拌器及兩個 進料幫浦之具有500毫升容積的玻璃反應器中。將内容物 加熱至8 0 C，並經2小時逐漸添加〇. 5公克第三戊基過氧 16 201100449 基（2-乙基己酸醋）（®Per〇Xan AP〇，pergan GmbH ) 、5 公 克乙酸乙醋、另外5〇公克異丙醇、36〇公克丙稀酸丁醋、 14·0公克丙_ 乙基己S旨與6·8〇公克甲基丙稀酸環氧乙 烷基甲酯之混合物》將混合物在攪拌下保持在8{rc下另外 1小時，並接著將〇·5公克第三戊基過氧基（2_乙基己酸醋）、 5公克異丙醇、20公克乙酸乙醋、丨5.2公克丙烯酸丁酯、 6.0公克丙烯酸2-乙基己酯與2·〇公克曱基丙烯酸環氧乙烷in. The reaction is then brought to 1% by maintaining the mixture at reflux temperature for an additional one and a half hours or more and the residual monomer, solvent and by-products decomposed from the base initiator are finally removed by distillation under reduced pressure. The resulting polymer was cooled to 65 C and filtered through a filter having a pore size of 25 μm. The polymer obtained with a yield of 99.1% is light yellow and viscous, and has a weight average molar mass of η 2 ng 2 / mol, as determined by gel permeation chromatography using polystyrene standards . The polymer is called , uv_ i 〃. The mass fraction of the 2-hydroxybenzophenone moiety in this polymer was 2% by mass. Example 2: Preparation of a polymerized light stabilizer modified with decane 50 gram of isopropyl alcohol was charged into a glass reactor having a volume of 500 ml equipped with a reflux condenser, a stirrer and two feed pumps. The contents were heated to reflux and gradually added 〇.7 g of a third amyl peroxy (2-ethylhexanoate) (® LUpers〇i 575, Pennwalt Corp.), 140 g of ethyl acetate over 2 hours. , 5 grams of isopropanol, 50.1 grams of butyl acrylate, 2 gram of 2-ethylhexyl acrylate, 3.9 grams of vinyl terminated polyoxynoxy and 26 grams of 2-hydroxy-4-[2-propene A mixture of oxy]-ethoxyphenyl)-phenyl ketone (an ethylenically unsaturated substituted diphenyl ketone). Mixture 13 201100449 was maintained at reflux temperature for an additional 1 hour with stirring, and then 〇6 g of a second amyl sulfhydryl group (2-ethylhexanoate), 5 gram of isopropanol, 21.4 gram of propylene A second mixture of butyl vinegar and 8.6 grams of 2-ethylhexyl acrylate was added to the reaction mixture over a further 2 hours. The reaction is then completed by maintaining the mixture at reflux temperature for an additional one and a half hours or more, and finally the residual monomer, solvent and by-products from the decomposition of the base initiator are removed by distillation under reduced pressure. The resulting polymer was cooled to 65. (: and filtered through a filter with a 25 micron pore size. The polymer obtained with a yield of 98.8% is light yellow and viscous, and has a weight average molar stem of 125 kg/mole, such as to coagulate Gel permeation chromatography was determined using polystyrene standards. The polymer was referred to as UV 2 。. The mass fraction of the 2-hydroxy hydroxy group in this polymer was 20%. Example 3: Coatings The preparation of the coating composition based on the acrylic binder resin was prepared according to the formulation of Table 1. These compositions were used as the polymerizable stabilizers of Examples 1 and 2 (UV-1 and Uv_2) and the conventional diphenyls. A ketone-type light stabilizer (,, comparative, 2-hydroxy-4-(2-ethylethoxy)-diphenyl ketone) is stabilized, including unreacted samples as a reference. These coating compositions are coated. Covered with cold-rolled steel sheets that have been subjected to CED (cathode electrodeposition) primer treatment and white primer film, obtained at 14 (TC after 3 minutes drying from 牦 micron to 5 〇 micron mil to 2. mil) Dry Film Thickness 14 201100449 Table 1: Coating Compositions A to D + ABC Acrylic Resin * 75 75 grams 75 grams 75 grams melamine crosslinker resin ++ 25 grams 25 grams 25 grams 25 grams acid catalyst (DDBSA) $ 0.7 grams 0.7 grams 0.7 grams 0.7 grams UV-1 (Example 1) 1 gram 0 0 0 UV-2 (Example 2) 0 1 gram 0 0 Comparative light stabilizer 0 0 2 gram 0 HALSQ 1 gram 1 gram 1 gram 0 〇 + butanol (15 grams), diphenyl (18 grams) and PM A solvent mixture of acetate (propylene glycol monoterpene ether acetate, 18 grams) is added to all formulations * Hydroxy-functional acrylic resin dissolved in a mixture of alkylated aromatics - Solvent Naphtha, 65% Mass fraction solid, 22 mg/g acid value, 120 mg/g hydroxyl value ++ highly methylated melamine formaldehyde resin, 3800 mPa.s at 25 ° C, less than 0.3% by mass Free aldehyde oxime $ DDBSA = dodecyl benzene sulfonate α 1,2,2,6,6-pentamethyl-4-piperidinol mono- and di-ester and azelaic acid mixture (® Tinuvin 262, Ciba Specialty Chemicals Inc.) The mass fraction of the 2-hydroxydiphenyl ketone moiety is 0.2% for both coating compositions a and B. The coating composition C was 2.0%, and the composition D was a control group which was not stabilized. These coated steel sheets (the steel sheet A coated with the coating composition A and the steel sheet B coated with the coating composition B were used as the coating composition). c coated steel 15 201100449 plate C 'coated steel plate D coated with coating composition D) subjected to the test according to ASTM G 1 5 5 (at 0.3 5 watts / square meter and (6 3 ± 3 ) ° C ; irradiation for 102 minutes followed by irradiation with water spray for 18 minutes). The yellowing change in the film was monitored after the specified exposure time and the results were collected in Table 2. The yellowing (Δ b ) is measured by a conventional instrument (b YK Gardner spectrophotometer) and calculated according to ASTM E 3 1 3 . Table 2: Yellowing change after irradiation (Δ b) Ab after the right column time 500 hours 1000 hours 1500 hours 2000 hours 3000 hours 4000 hours 5000 hours Steel plate A 0.09 0.29 0.34 0.49 0.6 0.8 0.94 Steel plate B 0.1 0.35 0.37 0.49 0.6 0.7 0.88 Steel plate C 0.35 0.66 0.73 0.91 1.2 1.4 1.67 Steel plate D 0.56 1.31 2.06 3.39 8.4 Not 4 Bug can be observed although the mass fraction of the stable structure 2-hydroxydiphenyl ketone in the coating compositions A and B is only It is 1%% of the coating composition C (here, the mass fraction of 2%), but it is far from the yellowing caused by ultraviolet light in the coating composition containing the conventional ultraviolet stabilizer. This protection is lower in the coating compositions Α and Β than the examples of the UV stabilizer according to the invention. Example 4: Preparation of a polymerized light stabilizer based on stupid triazole 70 g of isopropanol was poured into a glass reactor having a volume of 500 ml equipped with a reflux condenser, a stirrer and two feed pumps in. The contents were heated to 80 C and gradually added over 2 hours. 5 g of the third amyl peroxy 16 201100449 base (2-ethylhexanoic acid vinegar) (® Per〇Xan AP〇, pergan GmbH), 5 Acetic acid ethyl acetate, another 5 gram gram of isopropyl alcohol, 36 gram gram of acrylic acid butyl vinegar, 14,000 grams of propyl _ ethyl hexyl s and 6.8 gram grams of methyl acrylate oxirane Mixture of esters. The mixture was kept under stirring at 8{rc for an additional hour, and then 〇5 g of a third amyl peroxy group (2-ethylhexanoic acid vinegar), 5 g of isopropanol, 20 Acetic acid ethyl acetate, 丨 5.2 grams of butyl acrylate, 6.0 grams of 2-ethylhexyl acrylate and 2·〇 grams of methacrylic acid ethylene oxide
基甲酿之第二混合物在另外1小時期間内添加至反應混合 物中。反應接著藉由將混合物保持在8(rc下i小時以上而 達到元成’且敢终將殘餘單體、溶劑及來自基起始劑分解 的副產物在減壓下以蒸餾移出。所得聚合物接著溶解在2〇 公克二曱苯中及加熱至150°C。添加20.0公克3-[3-(2H-苯 并二唑-2-基）-5-第三丁基-4-羥苯基丙烯酸（酸官能性苯并 三。坐’ CAS# 84268-36-0)且維持溫度，直到反應混合物的 酸值少於3毫克/公克（根據DIN EN ISO 2114所測量）為 止。添加更多二甲苯，以獲得5〇%之質量分率的固體。所 得聚合物具有11.3公斤/莫耳之重量平均莫耳質量，如以凝 膠滲透層析術使用聚苯乙烯標準所測定。聚合物被稱為 、、UV-3〃 〇 實施例5 :酸官能性三啡中間物之製備 [4-[4,6_雙（2,4_二曱基苯基）I3，％三啡_2基]_3_羥苯氧基]_ 乙酸乙酯之合成 化合物[4-(4,6-雙（2,4-二甲基苯基）-1，3,5-三明^2-基）-3-翻苯氧基]-乙酸乙酯係採用US 6,265，576中所述之程序（第 17 201100449 40段’化合物A)而合成，其中將8〇〇公克2_(2,4_二羥苯 基）-4,6-雙（2,4-二曱基苯基三啩在6(TC下與270公 克氣乙酸乙醋在含有692公克無水碳酸鉀作為酸清除劑及 33.2公克硬酸鉀作為觸媒的5〇0〇毫升丙酮溶劑中反應9小 時。將實施例中所述之粗產物從等質量的二氯甲烷與甲醇 之混合物再結晶，獲得純化之[4-[4,6-雙（2,4-二甲基苯 基）-1，3,5·二啡_2_基]_3_羥苯氧基]_乙酸乙酯。 實施例6 :以羥芳基三啡為基之聚合性光安定劑之製備 將80公克異丙酵裝入配備回流冷凝器、攪拌器及兩個 進料幫浦之具有500毫升容積的玻璃反應器中。將内容物 加熱至回流’並經2小時逐漸添加〇. 6公克第三戊基過氧基 (2-乙基己酸酯）（®Per〇xan apo，pergail GmbH )、40 公克 乙酸乙醋、36.0公克丙烯酸丁酯、14.〇公克丙烯酸2-乙基 己醋、5.0公克甲基丙烯酸環氧乙烷基甲酯與ι 〇公克以乙 稀基終止之聚二甲基矽氧烷之混合物。將混合物在攪拌下 保持在回流溫度下另外1小時’並接著將〇.4公克第三戊基 過氧基（2-乙基己酸酯）、3〇公克乙酸乙酯、16.2公克丙烯酸 丁醋、0.0公克丙烯酸2-乙基己酯與1.8公克甲基丙烯酸環 氧乙烷基f酯之第二混合物在另外丨小時期間内添加至反 應混合物中。反應接著藉由將混合物保持在回流溫度下1 小時以上而達到完成，且最終將殘餘單體、溶劑及來自基 起始劑分解的副產物在減壓下以蒸餾移出。接著將所得聚 合物/容解在25公克二甲苯中及加熱至15〇。匚。添加20.0公 克來自實施例5之中間物（[4-[4,6-雙（2,4-二甲基苯 18 201100449 基卜1’3,5-三畊-2-基]-3·羥苯氧基]-乙酸）且維持溫度，直到 反應混合物的酸值少於3毫克/公克（根據dinenis〇2U4 所測量）為止。添加更多二甲苯，以獲得5〇%之質量分率 的固體。聚合物具有ια·8公斤/莫耳之重量平均莫耳質量， 如以凝膠滲透層析術使用聚苯乙烯標準所測定。聚合物被 稱為、UV-4# 〇 實施例7 :塗料之製備 以丙烯酸黏合劑樹脂為太之塗料組成物Ε、F、G和Η 係根據表3之調配物製備。將這些組成物以實施例4和6 (UV-3和UV-4 )之聚合性安定劑及以習知的苯并三唑型光 安定劑（®Tinuvin 1130，Ciba Specialty Chemicals)安定， 以未安定化之樣品作為參考。將這些塗料組成物塗覆於曾 以金屬底漆膜塗布之冷軋鋼薄片，在8(TC經30分鐘乾燥之 後得到從20微米至30微米之乾膜厚度。 _ 表3 :塗料調配物 組分+ Ε F G Η 丙烯酸樹脂* 80公克 80公克 80公克 805公克 丙稀酸流動劑++ 2公克 2公克 2公克 2公克 聚矽氧流動劑本 2公克 2公克 2公克 2公克 DBTL (1%) ** 0.5公克 0.5公克 0.5公克 0.5公克 UV-3 1.5公克 - - UV-4 - 1.5公克 - - 比較性 - - 1.5公克 - 光安定劑+++ HALS*** 0.7公克 0.7公克 0.7公克 0.7公克 聚異氰酸酯ί ί 37.7公克 37.7公克 37.7公克 37.7公克 201100449 +將二m酸醋（4公克）、芳香族烴（4公克）、、、pM乙酸 S曰（丙一醇單甲醚乙酸酯，4公克）與乙酸丁酯（2·8公 克）之溶劑混合物添加至所有的調配物中 *溶解在乙酸丁酯中的羥基官能性丙烯酸樹脂，7〇%之質量 分率的固體，151毫克/公克之羥基值 ++>谷解在乙酸丁酯中的羥基官能性丙烯酸流動改良劑，i 〇 %之質量分率的固體 ί溶解在乙酸丁 S旨中的改良之聚矽氧，1〇%之質量分率的 固體 **在乙酸丁酯中的二月桂酸二丁基錫溶液（〇〇8%之質量分 率的錫）， + + +苯并三唑型光安定劑（®Tinuvin 1130，ciba Specialty Chemicals ) 受阻胺光安定劑（®Tinuvin 292，Ciba Specialty Chemicals )The second blend of the base was added to the reaction mixture over a further one hour period. The reaction is then carried out by maintaining the mixture at 8 (rc for more than i hours) and the residual monomer, solvent and by-products decomposed from the base initiator are removed by distillation under reduced pressure. Then dissolved in 2 gram of diphenylbenzene and heated to 150 ° C. Add 20.0 grams of 3-[3-(2H-benzobisazol-2-yl)-5-tert-butyl-4-hydroxyphenyl Acrylic acid (acid functional benzotriene. sit 'CAS # 84268-36-0) and maintain the temperature until the acid value of the reaction mixture is less than 3 mg / g (measured according to DIN EN ISO 2114). Add more two Toluene to obtain a mass fraction of 5% by mass. The resulting polymer had a weight average molar mass of 11.3 kg/mol, as determined by gel permeation chromatography using polystyrene standards. 、, UV-3〃 〇 Example 5: Preparation of acid functional trimorphine intermediate [4-[4,6-bis(2,4-diphenylphenyl) I3, % trimorphin-2-yl] Synthesis of _3_hydroxyphenoxy]-ethyl acetate [4-(4,6-bis(2,4-dimethylphenyl)-1,3,5-trim-yl-2-yl)-3- Diphenoxy]-ethyl acetate is US 6,265 Synthesis of the procedure described in 576 (Section 17 201100449, paragraph 40 'Compound A), wherein 8 〇〇g 2_(2,4-dihydroxyphenyl)-4,6-bis(2,4-didecyl) Phenyltrifluoride was reacted at 6 (TC) with 270 g of gaseous acetic acid in acetic acid in a solvent of 5 〇 0 ml of acetone containing 692 g of anhydrous potassium carbonate as an acid scavenger and 33.2 g of potassium citrate as a catalyst. The crude product described in the examples is recrystallized from an equal mass of a mixture of dichloromethane and methanol to give purified [4-[4,6-bis(2,4-dimethylphenyl)-1,3, 5·Dimorpho-2-yl]_3_hydroxyphenoxy]-ethyl acetate. Example 6: Preparation of a polymerizable light stabilizer based on hydroxyaryl trimorphine 80 g of isopropyl yeast was charged The reflux condenser, the agitator and the two feed pumps were placed in a glass reactor having a volume of 500 ml. The contents were heated to reflux' and gradually added 〇. 6 g of the third amyl peroxy group (2 g) -ethylhexanoate) (®Per〇xan apo, pergail GmbH), 40 g of ethyl acetate, 36.0 g of butyl acrylate, 14. g of acrylic acid 2-ethylhexyl vinegar, 5.0 g of methacrylic acid epoxy a mixture of ethyl ethane methyl ester and dimethyl hydrazine terminated by a vinyl group. The mixture is maintained at reflux temperature for an additional 1 hour while stirring. 4 g of the third pentyl group is then added. Peroxy (2-ethylhexanoate), 3 g of ethyl acetate, 16.2 g of butyl acrylate, 0.0 g of 2-ethylhexyl acrylate and 1.8 g of oxiranyl methacrylate The two mixtures were added to the reaction mixture over a further one hour. The reaction is then completed by maintaining the mixture at reflux temperature for more than 1 hour, and finally the residual monomer, solvent and by-products from the decomposition of the base initiator are removed by distillation under reduced pressure. The resulting polymer was then taken up in 25 g of xylene and heated to 15 Torr. Hey. 20.0 grams of the intermediate from Example 5 was added ([4-[4,6-bis(2,4-dimethylbenzene 18 201100449 kib 1 '3,5-trin-2-yl]-3·hydroxyl Phenoxy]-acetic acid) and maintained at a temperature until the acid value of the reaction mixture is less than 3 mg/g (as measured by dinenis® 2U4). Add more xylene to obtain a mass fraction of 5% by mass. The polymer has a weight average molar mass of ια·8 kg/mol, as determined by gel permeation chromatography using polystyrene standards. The polymer is referred to as UV-4# Example 7: Coating The preparation was carried out using an acrylic binder resin as the coating composition of Ε, F, G and lanthanides according to the formulation of Table 3. The polymerization of these compositions was carried out as in Examples 4 and 6 (UV-3 and UV-4). The stabilizer is stabilized with a conventional benzotriazole-type light stabilizer (® Tinuvin 1130, Ciba Specialty Chemicals), and the unstabilized sample is used as a reference. These coating compositions are applied to a metal primer film. Coated cold-rolled steel sheets obtained a dry film thickness of from 20 μm to 30 μm after drying for 8 minutes on TC. _ Table 3: Coatings Formulation component + Ε FG Η Acrylic resin * 80 grams 80 grams 80 grams 805 grams of acrylic acid flow agent ++ 2 grams 2 grams 2 grams 2 grams of polyoxyl flow agent 2 grams 2 grams 2 grams 2 grams DBTL ( 1%) ** 0.5g 0.5g 0.5g 0.5g UV-3 1.5g - - UV-4 - 1.5g - - Comparative - - 1.5g - Light stabilizer +++ HALS*** 0.7g 0.7g 0.7 Gram 0.7 g polyisocyanate ί ί 37.7 g 37.7 g 37.7 g 37.7 g 201100449 + 2 m acid vinegar (4 g), aromatic hydrocarbon (4 g), pME acetic acid S 曰 (propanol monomethyl ether acetate A solvent mixture of ester, 4 g) and butyl acetate (2.8 g) was added to all formulations * hydroxy-functional acrylic resin dissolved in butyl acetate, 7% by mass solids, 151 Mn/kg hydroxy value++> hydroxy-functional acrylic flow improver in butyl acetate, i 〇% mass fraction of solid ί dissolved in butyl acetate 1% by mass of solids** of lauric acid in butyl acetate Dibutyltin acid solution (〇〇 8% by mass of tin), + + + benzotriazole type photo stabilizer (® Tinuvin 1130, ciba Specialty Chemicals) Hindered amine light stabilizer (® Tinuvin 292, Ciba Specialty Chemicals )
t ί以HDI為基之聚異氰酸酯，75%之質量分率的固體’ 16.5%之質量分率的NCO 在組成物E中的苯并三唑部分之質量分率與組成物E 中的該部分相比約為5倍。組成物Η為未安定化之控制組。 使這些塗布之鋼板（以塗料組成物Ε塗布之鋼板Ε，以塗料 組成物F塗布之鋼板F，以塗料組成物G塗布之鋼板G，以 塗料組成物Η塗布之鋼板Η )接受QUV耐候試驗（Q-Lab， 波長：3 13奈米，在5(TC下照射4小時及接著在40°C下水 20 201100449 喷霧4小時之循環）。在塗膜中的黃化變化係在指定之暴 露時間之後監控，將結果收集於表2中。 黃化（△ b )係以慣用的儀器（b YK Gardner分光光度 計）測量且根據ASTM E 3 13計算。 表2 :在照射之後的黃化變化（△匕) 在右列時間 之後的Ab 168 小時 336 小時 504 小時 672 小時 840 小時 鋼板A 1.54 1.98 2.16 2.45 2.85 鋼板B 1.62 1.78 1.80 2.20 2.51 鋼板C 1.48 1.85 2.26 2.28 2.54 鋼板D 1.74 2.55 2.94 3.36 4.51 可觀察到雖然在塗料組成物E中的安定結構苯并三唑 之質量分率僅為塗料組成物G的20%，但是由紫外光所引 起之黃化就兩個鋼板而言係在相同的範圍内。亦可觀察到 塗料組成物F (含有以三畊型光安定劑化學結合至兩親性聚 〇 合物）顯示出比其他鋼板更少的黃化。 實施例7 :用於水可分散之聚合性光安定劑之製備 將164公克乙酸甲氧基丙酯及271.5公克3-[3-(2H-苯 并三唑-2-基）-5-第三丁基-4-羥苯基]丙酸（酸官能性苯并三 唑’ CAS# 84268-36-0)裝入配備回流冷凝器及攪拌器之具 有1000毫升容積的玻璃反應器中。添加0.5公克氫醌單甲 醚及113.7公克縮水甘油甲基丙烯酸酯且加熱至多130°C， 同時以穩定起泡之空氣經過反應混合物。維持反應溫度， 直到酸值少於5毫克/公克（根據DIN EN ISO 2114所測量） 21 201100449 為止。所得產物具有72%之質量分率的固體。 實施例8 :水可分散之聚合性光安定劑 將78公克正丁酵及18公克甲氧基丙醇裝入配備回流 冷凝器、授拌器及兩個進料幫浦之具有500毫升容積的玻 璃反應器中。將内容物加熱至11 5。(：，並經6小時逐漸添加 1.0公克第三丁基過氧化物、6.5公克正丁醇、29.0公克丙 烯酸丁酿、1〇.〇公克丙烯酸、30公克丙烯酸羥乙酯、3,〇 公克丙稀酸全氟烧基乙酯（®Fluowet AC 600，Clariant Deutschland GmbH )與40公克實施例7的產物之混合物。 將混合物在攪拌下保持在115。(：下另外2小時，並接著將 0.2公克第三戊基過氧化物與丨.〇公克正丁醇之第二混合物 添加至反應混合物中。反應接著藉由將混合物保持在^ $ c下1小時以上而達到完成。接著將溫度減低至8〇艺，並 添加12公克N，N-二曱基乙醇胺及2〇公克去離子水。添加 更多去離子水調整固體的質量分率至48%。獲得具有86 之pH (在具有10%之質量分率的固體之水溶液上所測量） 及6400 mPa.s之動態黏度的黃色澄清溶液。 將鋼板以在分散液令每80公克丙烯酸樹脂固體計具有 1.5公克安定劑樣品之丙烯酸樹脂水性分散液塗布，接受在 實施例6中所述之耐候試驗。在照射7〇〇小時之後，^黃 化變化測量得到2.5之值。此性能類似於攜載溶： 之樹脂所顯示者。 【圖式簡單說明】 22 201100449 無 【主要元件符號說明 無t ίHDI-based polyisocyanate, 75% by mass of solids. 16.5% by mass of NCO. The mass fraction of the benzotriazole moiety in composition E and the fraction in composition E. Compared to about 5 times. The composition is a control group that is not stabilized. These coated steel sheets (the steel sheet coated with the coating composition, the steel sheet F coated with the coating composition F, the steel sheet G coated with the coating composition G, and the steel sheet coated with the coating composition Η) were subjected to the QUV weathering test. (Q-Lab, Wavelength: 3 13 nm, cycled at 5 (TC for 4 hours and then at 40 °C for 20 201100449 spray for 4 hours). The yellowing change in the coating is specified at exposure After the time monitoring, the results were collected in Table 2. The yellowing (Δb) was measured with a conventional instrument (b YK Gardner spectrophotometer) and calculated according to ASTM E 3 13. Table 2: Yellowing changes after irradiation (△匕) Ab 168 hours after the right column time 336 hours 504 hours 672 hours 840 hours Steel plate A 1.54 1.98 2.16 2.45 2.85 Steel plate B 1.62 1.78 1.80 2.20 2.51 Steel plate C 1.48 1.85 2.26 2.28 2.54 Steel plate D 1.74 2.55 2.94 3.36 4.51 It was observed that although the mass fraction of the stable structure benzotriazole in the coating composition E was only 20% of the coating composition G, the yellowing caused by the ultraviolet light was in the same range for the two steel sheets. Inside. It was observed that the coating composition F (containing chemically bonded to the amphiphilic polyconjugate with a three-till photo-stabilizer) showed less yellowing than other steel sheets. Example 7: Polymerizability for water dispersibility Preparation of light stabilizer 164 g of methoxypropyl acetate and 271.5 g of 3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionic acid (Acid-functional benzotriazole 'CAS # 84268-36-0) was charged into a glass reactor with a volume of 1000 ml equipped with a reflux condenser and a stirrer. 0.5 g of hydroquinone monomethyl ether and 113.7 g of glycidol were added. The methacrylate is heated up to 130 ° C while passing the stabilized foaming air through the reaction mixture. The reaction temperature is maintained until the acid value is less than 5 mg / g (measured according to DIN EN ISO 2114) 21 201100449. A solid having a mass fraction of 72%. Example 8: Water-dispersible polymerizable light stabilizer 78 kg of n-butyl fermentation and 18 g of methoxypropanol were charged with a reflux condenser, a stirrer and two The feed pump has a 500 ml volume glass reactor. The contents are heated. 11 5. (:, and gradually add 1.0 grams of third butyl peroxide, 6.5 grams of n-butanol, 29.0 grams of acrylic acid, 1 〇. gram of acrylic acid, 30 grams of hydroxyethyl acrylate, 3, over 6 hours. A mixture of perfluoroacetic acid perfluoroalkyl ester (® Fluowet AC 600, Clariant Deutschland GmbH) and 40 grams of the product of Example 7. The mixture was maintained at 115 with stirring. (: another 2 hours, and then a second mixture of 0.2 g of the third pentyl peroxide and ruthenium gram n-butanol is added to the reaction mixture. The reaction is then held at ^ c c The completion is completed over a period of time. Then the temperature is reduced to 8 〇, and 12 grams of N,N-dimercaptoethanolamine and 2 gram grams of deionized water are added. Add more deionized water to adjust the mass fraction of the solid to 48%. Obtain a yellow clear solution with a pH of 86 (measured on an aqueous solution having a mass fraction of 10%) and a dynamic viscosity of 6400 mPa.s. The steel plate is made per 100 grams of acrylic solids in the dispersion. The aqueous dispersion of acrylic resin having a sample of 1.5 gram of stabilizer was coated and subjected to the weathering test described in Example 6. After 7 hours of irradiation, the change in yellowing was measured to obtain a value of 2.5. This property is similar to carrying Solvent: The resin is displayed. [Simplified illustration] 22 201100449 No [Main component symbol description No